Derivatives of 2-aminc-diphenylsulfone



' mono-carboxy phenyl.

- by heating a mixture of a Patented June 15, 1948 DERIVATIVES OF Z-AMINO- DIPHENYLSULFONE Donovan E.

to E. I. du Pont Kvalnes, Penna Grove, N. 3., assignor de Nemours 8a Company, Wilmington, Del., a corporation of Delaware No Drawing. Application October 2, 1942, Serial No. 460,535

1 Claim. (Cl. 260-397.6)

This invention relates to new amino-diphenylsulfone derivatives, and especially to a class of 2-amino-dipheny1sulfone derivatives. The new compounds are useful for various purposes, and especially as intermediates for azo dyes.

Heretofore various 2-nitroand Z-amino-diphenylsulfone derivatives were known, such as those in which the nucleus substituted by amino is additionally substituted by amino, nitro or -N- acetyl, and those in which the phenylsulfone nucleus is substituted by-sulfonic acid; but in so far as I am aware, no 2-amino-diphenylsulfone compounds were known wherein the phenylsulfonyl nucleus is substituted by an amine group comprising a -CO-Alkyl, --COOAlkyl, -CO--Aryl, or -SOz--Aryl group. The latter compounds are useful as diazo components for the manufacture of monazo wool dyes having unexpected dyeing and fastncss properties.

It is among the objects of the present invena tion to provide 2-amino-diphenylsulfone derivatives which are represented in general by the formula Q Q Ill-X NH: Y

.inafter defined, and Y represents phenylsulfone, tolylsulfone and naphthylsulfone, wherein alkyl is from a group consisting of saturated and unsaturated aliphatic groups having 1 to 2 carbons and the mono-chloro, -phenyl, -phenoxy and -carboxy derivatives thereof and aryl is from a group consisting of phenyl, tolyl, mono-chloro phenyl, mono-sulfo phenyl and Other objects of the invention will be apparent from the following description.

The objects of the invention may be attained benzene sulflnic acid which is substituted by the desired -NXY group and an ortho-nitro-chlorobenzene in the presgroup either directly ence of an acid acceptorto form the 2-nitro derivative, and then reducing the nitro group. The objects may also be attained in general by reducing an orthoor para-nitro-chlorobenzene with NaSI-I in aqueous solution made alkaline with sodium hydroxide until a compound is produced which is repres-entedioy the formula fla and then reacting with ortho-nitro-chlorobenzene to form the compound represented in general by the formula The latter compound is then reacted with an appropriate acid chloride or anhydride to form the desired substituted -NXY group, and then the resulting substituted diphenyl sulfide is oxidized to the corresponding diphenylsulfone by the action of hydrogen peroxide in glacial acetic acid medium. Finally the nitro group is reduced to amino. The alkylated sulfone amide group is formed by suitable alkylation of the sulfonamide before or directly after the oxidation to the diphcnylsulfpne. This second method is generally applicable only to the production of 'sulfones in which the amide substitu'ent is in the ortho or para position in respect to the sulfone group.

The invention will be more fully set forth in the following more detailed description which includes examples that are given as illustrative embodiments of the invention and tions thereof. Parts are expressed in parts by weightunless otherwise noted.

Example 1 Two hundred parts of p-acetylaminobenzene sulilnic acid, 158 parts of o-nitrochlorbenzene, 82 parts of sodium acetate (or 96 parts of potassium acetate) and 500 parts of methyl alcohol not as limita- C. and stirred nitro-4'-acetylamino-diphenylsulfone thus formed is 245-247 C. Hydrogenation in alcohol with a nickel catalyst yields the amino compound onto ONHOSOr-Q NH: v which has a melting point of 237-239 C. following recrystallization from alcohol or acetic acid.

Instead of o-nitrochlorbenzene an equivalent amount of o-nitro-brombenzene can be used.

Instead of carrying out the reaction in an autoclave with methyl alcohol as the solvent, the same reaction may be eifected by using a solvent such as cyelohexanol, the monomethyl ether of ethyl-- ene glycol and similar solvents and heating to the reflux temperature of the solution.

Example 2 2-amino-3'-acetylaminodiphenylsulfone is obtained by substituting an equal weight of m-acetylaminobenzene sulfinic acid for the para derivative used in Example 1.

Example 3 tained for 1 /2 to 2 hours at which time only a 4 by the method of Example 1. Upon catalytic reduction, it gives 2-amino-4-acetylaminodiphenylsulione which is identical with that described in Example 1.

Example 4 aniline. The mixture is filtered and the residue is washed with dilute acid. The residue is dissolved in dilute sodium hydroxide solution, fil- I tered and the filtrate made acid by adding concentrated hydrochloric acid. The insoluble material is filtered oil, washed and dried. The melting point of the 2-nitro-4'-p-toly1 sulfonylaminodiphenylsulfidethus formed is 168 C. This material is oxidized to give 2-nitr0-i'-p-to1ylsulfonylaminodiphenylsulfone by the same procedure as that described in Example 3. Catalytic reduction gives 2-amino-4'-p-tolyl sulfonylaminodiphenyltrace of sulfide remains. The mixture is filtered and 315 g. of o-nitrochlorbenzene are added to the hot filtrate. This mixture then is refluxed for 16 hours and finally is subjected to steam distillation to eliminate any unchanged o-nitrochiorbenzene. The 2-nitro-4'-aminodiphenylsulfide thus formed is obtained by filtration subsequent to cooling. The melting point of the recrystallized yellow compound is 106 C.

One mole (246 g.) of 2-nitro-4'-aminodiphenyl- Sulfide is suspended in 400 g. of glacial acetic acid and 110 g. of acetic anhydride are added. The mixture is refluxed for about four hours, cooled and drowned on ice and filtered. The'dry product is recrystalized from acetic acid and has a melting point of 199-200 C. Its formula is One mole (286 g.) of this product is suspended in 800 g. of glacial acetic acid, heated to 100 C.

and allowed to cool to 25 C. Five hundred cubiccentimeters of 30% hydrogen peroxide are added and the mixture is allowed to stand at room temperature for two hours The temperature is then slowly raised to 50 C. and maintained at this point for two hours. Then 200 cc. of 30% hydrogen peroxide are added and the temperature is sulfone.

Example 5 A solution of 432 parts of 2-m'tro-4'-p-tolyl sulfonylaminodiphenylsulfone (prepared as described in Example 4) in dilute sodium hydroxide solution is heated to C. Then 126 parts of dimethyl sulfate are added gradually over two hours, during which time the reaction mixture is maintained alkaline by adding sodium hydroxide from time to time. After maintaining the mixture two to three hours at 75 C., an alkali insoluble material is formed and this is filtered from the hot solution. This material is recrystallized from alcohol giving 2-nitro-4'-(p-tolyl sulfonyl methyl amino) diphenylsulfone (M. P. 146 C.) which is represented by the formula I Nor Catalytic reduction yields the corresponding 2-amino derivative (M. P. 169 C.).

Example 6 By using an equal weight of o-nitrochlorbenacne in place of the p-nitrochlorbenzene in the yields 2-nitro-2'-acetylaminodiphenylsulfone' (M.

P. 182 C.), which on catalytic reduction gives 2-amino-2-acetylaminodiphenylsulfone (M. P. 149 C.). The latter product is represented by the formula NHCOCH;

Example 7 The use of an equivalent amount of propionic anhydride instead of the acetic anhydride used in Example 3 yields 2- nitro-4'-propionyl aminodiphenylsulfide (M. P. 145 0.). Oxidation and reductioni-n the manner similar to that already described yields 2 amino 4 propionylaminodi- 2-amino 4' phthaloylaminodiphenylsulfone,

28A 2amino-4'beta-naphthyl-sulfonylamino diphenylsulfone,

29 2 amino 4' beta naphthoylaminodi phenylsulfone,

29A 2 amino 3'para-tolylsulfonylaminod'iphenylsulfone,

30 2 amino 3 chloracetylaminodiphenylsulfone,

31 2-amino-3'benzoylaminodiphenylsulfone,

32 2 amino 2' chloracetylaminodiphenyl sulfone,

33 2-amino-2'benzoylaininodiphenylsulfone,

34 2 amino 2' benzene sulfonylamlnodi phenylsulfone,

2' amino 4'-paratolyl-sulfonybsulfatoethylaminodiphenylsulfone,

36 2 amino-4'-para-tolyl-sulfonyl-carboxyethylaminodiphenylsulfone,

37 2-amino-4' (carboethoxy ethylamino) diphenylsulfone, 1

38 2-amino-4' (benzoyl ethylamino) diphenylsulfone.

In the specification and claim, the term, substituted alkyl groups refers to methylor ethylmonosubstituted by OH, 30311, OSOaH, COOH or- CeHs, such as C2H4OH,

The described 2-aminodiphenylsulfone tives diazotized and coupled in acid medium with 2amino6-sulfo-8-naphthol, or its N-alkyl derivatives, yield dyes which on wool give red shades of good fastness to light and wet treatments. Dee

- pending on their structure, the dyes are eminently suited for dyeing wool under neutral conditions or under acid conditions.

This is a continuation-in-part of my copending application Serial No. 419,528, filed November 18, 1941, Patent No. 2,361,481, October 31, 1944.

From the foregoing disclosure it will be recognized that the invention issusceptlble of modification without departing from the spirit and scope thereof andit is to be understood that the invention is not restricted to the specific illustrations thereof herein set forth.

I claim:

A compound represented by the formul Donovan E. KVALNES.

REFERENCES crrEn The following references are of record in th I file of this patent:

phenylsulfone which is represented by the formula CHlCHaCONHGSOu-Q 7 NH:

Example 8 Reaction of 2-nitro-4'aminodiphenylsulfide in toluene with ethyl chlorocarbonate in a manner similar to that described in the foregoing examples produces 2-nitro-4carboethoxyaminodiphenylsulflde (M. P. 150-151 C.). Oxidation with 30% hydrogen peroxide in glacial acetic acid produces the sulfone. Reduction of the nitro group by catalytic means produces 2-amino-4'- carboethoxyaminodiphenylsulfone which is represented by the formula As illustrative of other products of the invention which are prepared by using the appropriate reactants in the manners described in the foregoing examples are mentioned:

Ei-kample 9 2-amino-4'benzoylaminodiphenylsulfone,

10 2-amino-4'-p-chlorbenzoylaminodiphenyl sulfone, 1

11 2-amino-4-carbomethoxyaminodiphenyl sulfone,

12 2 amino 4'-. benzene sulfonylaminodi phenylsulfone,

l3 2 amino-4'-p-tolyl sulfonylethylaminodiphenylsulfone,

14 2-amino-4-p-tolyl sulfonyl hydroxy ethylaminodiphenylsulfone,

15 2 amino 4' p tolyl sulfonyl carboxy methylaminodiphenylsulfone, Y I

16 2-amino-4-p-tolyl sulfonyl beta-sulfoethylaminodiphenylsulfone,

17 2-amino-4-benzene sulfonyl butylaminodiphenylsulfone,

18 2-amino-4'-benzene sulfonyl benzylaminodiphenylsulfone,

19 2 amino 4' alphachlorpropionyl butylaminodiphenylsulfone,

20 2-amino-3'-phenyl acetyl methylaminodiphenylsulfone,

21 2-amino-4'-acetyl methylaminodiphenylsulfone.

22 2-amino-3' (acetyl butylamino) diphenylsulfone,

23 2-amino-4'-[m-sulfobenzoyl amino] diphenylsulfone,

24 2-amino-4' chloracetylaminodiphenylsulfone,

25 2-amino-4'phenoxyacetyluminodiphenyl sulfone, I

26 2 amino 4' cinnamoylaminodiphenyl sulfone,

27 2 amino .4 succinoylaminodiphenyl sulfone,

UNITED- STATES PATENTS Number Name Date 2,192,828 Daniels Mar, 5, 1940 2,224,156 Kharasch et a1. Dec. 10, 1940 2,260,626 Kleiderer et a1 Oct. 28, 1941 OTHER REFERENCES Evans et aL, "Jour. Chem. Soc." 1935, pages 181-188.

Buttle at 9.1., "Biochem. Journ.

(1938), vol. 3: paces 1101-1110.

deriva- 

